CN106462065A - Resin composition containing polyimide precursor, method for manufacturing cured film, and electronic component - Google Patents

Resin composition containing polyimide precursor, method for manufacturing cured film, and electronic component Download PDF

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Publication number
CN106462065A
CN106462065A CN201580008033.3A CN201580008033A CN106462065A CN 106462065 A CN106462065 A CN 106462065A CN 201580008033 A CN201580008033 A CN 201580008033A CN 106462065 A CN106462065 A CN 106462065A
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formula
resin combination
film
composition
cured film
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Inventor
小野敬司
榎本哲也
大江匡之
铃木佳子
副岛和也
铃木越晴
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HITACHI CHEM DUPONT MICROSYS
HD MicroSystems Ltd
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HITACHI CHEM DUPONT MICROSYS
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means

Abstract

A resin composition containing (a) a polyimide precursor having a structural unit expressed in formula (1) shown below, and (b) a photopolymerizing compound having an ethylenically unsaturated group and an isocyanuric ring structure. In formula (1), R1 is a tetravalent organic group, and R2 is a divalent organic group. R3 and R4 are each independently hydrogen atoms, C1-20 alkyl groups, C3-20 cycloalkyl groups, or monovalent organic groups having an unsaturated carbon-carbon double bond.

Description

Comprise the resin combination of polyimide precursor, the manufacture method of cured film and electronics Part
Technical field
The present invention relates to comprising the resin combination of polyimide precursor, the manufacture method using its cured film and electronics Part.
Background technology
Along with the miniaturization of semiconductor integrated circuit, need the layer being referred to as low-k layer for reducing dielectric constant Between dielectric film.Low-k layer has emptying aperture structure, therefore there is mechanical strength and reduces this problem.In order to protect such machinery The weak interlayer dielectric of intensity, can use the cured film being formed by polyimide resin.It is desirable to thick film shape for this cured film Become second nature (be greater than or be equal to 5 μm), high elastic modulus (be greater than or be equal to 4GPa) such characteristic.But, adjoint Thick-film and high elastic modulus, stress after solidification increases, the warpage of semiconductor wafer becomes big, there is transport, chip solid Timing produces the situation of undesirable condition.
Method as making the cured film low stress being formed by polyimide resin, for example can enumerate makes with spy Determine the phthalic compounds of functional group and the method (such as patent documentation 1) of the polyamide of sour composition copolycondensation.So And, in recent years require to be solidified at low temperature, in the case of making above-mentioned polyamide carry out low-temperature setting, have in acquisition and fill There is room for improvement for the cured film aspect of point performance.
Prior art literature
Patent documentation
Patent documentation 1：International Publication WO2006/008991 publication
Content of the invention
In addition, for low stress, have studied the high polyimide precursor containing fluorine of i line transmitance.However, the present invention People etc. distinguishes through research, result：The solidification of gained after the resin combination comprising these polyimide precursors is heating and curing Film easily absorbs the organic solvent used in corrosion-resisting technics, thus can occur swelling.Mentioned here swelling, it is that polyamides is sub- When amine cured film impregnates certain time (such as 20 minutes) in the N-Methyl pyrrolidone of uniform temperature (such as 70 DEG C), solidification Film lyosoption, the phenomenon of volumetric expansion.
Even if it is an object of the present invention to provide also can in the case that the low temperature less than or equal to 300 DEG C is solidified Obtain low stress and the resin combination of low swelling cured film.
According to the present invention, it is possible to provide resin combination below.
1. a kind of resin combination, it comprises following (a) composition and (b) composition.
A () has the polyimide precursor of the construction unit represented by following formula (1),
[changing 1]
(in formula, R1For quadrivalent organic radical group, R2For divalent organic group.R3And R4It is each independently hydrogen atom, carbon former The alkyl of subnumber 1～20, the cycloalkyl of carbon number 3～20 or the monovalent organic group with carbon carbon unsaturated double-bond.)
B () has ethylene unsaturated group and the photopolymerizable compound of isocyanuric acid ring structure.
2. the resin combination according to 1, the R of above-mentioned formula (1)2Divalent organic group represented by following formula (2).
[changing 2]
(in formula, R5～R12It is each independently hydrogen atom, fluorine atom or monovalent organic group, R5～R12At least one For fluorine atom, methyl or trifluoromethyl.)
3. the resin combination according to 1 or 2, the R of above-mentioned formula (1)2Divalent organic base represented by following formula (3) Group.
[changing 3]
(in formula, R13And R14It is each independently fluorine atom or trifluoromethyl.)
4. the resin combination according to any one of 1～3, above-mentioned photopolymerizable compound comprises following formula (4) institute The structure representing.
[changing 4]
(in formula, R24For hydrogen atom or methyl, X is alkylidene, and n is 1～25 integer.)
5. the resin combination according to 4, above-mentioned photopolymerizable compound is the compound represented by following formula (5).
[changing 5]
(in formula, R21～R23It is each independently monovalent organic group, at least one is the base represented by above-mentioned formula (4) Group.)
6. the resin combination according to any one of 1～5, above-mentioned (b) composition is with respect to above-mentioned (a) composition 100 matter Amount part comprises 0.01～50 mass parts.
7. the resin combination according to any one of 1～6, comprises to irradiate generation freely using active ray further The compound of base is as (c) composition.
8. the resin combination according to 7, the compound that above-mentioned utilization active ray irradiates generation free radical is oxime ester Compound.
9. the resin combination according to any one of 1～8, comprises the optical polymerism beyond (b) composition further Compound is as (e) composition.
10. the resin combination according to 9, above-mentioned photopolymerizable compound is (methyl) acyclic compound.
A kind of 11. manufacture methods of cured film, it comprises：Resin combination any one of 1～10 is coated on On substrate and be dried and form the operation of film and the operation that above-mentioned film is carried out with heat treated.
A kind of 12. manufacture methods of pattern cured film, it comprises：Resin combination any one of 1～10 is applied Cloth and is dried and forms the operation of film on substrate；Above-mentioned film is irradiated after active ray, is developed and obtained pattern The operation of resin film；And above-mentioned patterned resin film is carried out with the operation of heat treated.
The cured film that the manufacture method of 13. cured film described in 11 obtains.
The pattern cured film that the manufacture method of 14. pattern cured films described in 12 obtains.
15. electronic units with the pattern cured film described in cured film or 14 described in 13.
Even if in accordance with the invention it is possible to provide also can in the case that the low temperature less than or equal to 300 DEG C is solidified Obtain low stress and the resin combination of low swelling cured film.
Brief description
Fig. 1 is an embodiment of the electronic unit (semiconductor device) being manufactured using the resin combination of the present invention Summary sectional view.
Specific embodiment
Hereinafter, enter to resin combination involved in the present invention with using the manufacture method of the cured film of this resin combination Row explanation.Wherein, the present invention is not limited by this embodiment.
The resin combination of the present invention comprises following (a) composition and (b) composition.
[(a) composition]
There is the polyimide precursor of the construction unit represented by following formula (1)
[changing 6]
(in formula (1), R1For quadrivalent organic radical group, R2For divalent organic group.R3And R4It is each independently hydrogen atom, carbon The alkyl of atomic number 1～20, the cycloalkyl of carbon number 3～20 or the monovalent organic group with carbon carbon unsaturated double-bond.)
[(b) composition]
There is ethylene unsaturated group and the photopolymerizable compound of isocyanuric acid ring structure
It was to carry out being heating and curing of polyimide precursor in 370 DEG C about of high temperature in the past, but the resin combination of the present invention Thing passes through to comprise (a) composition and both (b) compositions, even if thus situation about being solidified in the low temperature less than or equal to 300 DEG C Under also can to obtain stress low and be not likely to produce swelling cured film.In the case of not using (a) composition, using such as polyphenyl AndDuring azoles precursor, even and if with (b) composition, also low to stress and swelling effect.
Hereinafter, each composition of the resin combination of the present invention is illustrated.
(a) composition：There is the polyimide precursor of the construction unit represented by following formula (1)
R in formula (1)1It is derived from the structure of tetrabasic carboxylic acid as raw material or its dianhydride.Stress, i line from cured film From the viewpoint of transmitance, R1Any one of group preferably represented by following formula (2a)～(2e).
[changing 7]
(in formula (2d), X and Y represents the divalent group or singly-bound not being conjugated with the phenyl ring being combined independently of one another.Formula (2e), in, Z is ehter bond (- O-) or thioether bond (- S-).)
" divalent group not being conjugated with the phenyl ring being combined " of X and Y of formula (2d) is, for example ,-O- ,-S- or following formula Represented divalent group.
[changing 8]
(in formula, R12For carbon atom or silicon atom.
R13It is each independently the halogen atoms such as hydrogen atom or fluorine atom.)
Wherein, R1More preferably derive from pyromellitic acid anhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride or 3,3 ', 4,4 '-connection The structure of benzene tertacarbonic acid's dianhydride.They can be used alone or are used in combination of two or more.
Do not make in the range of the stress of cured film, i line transmitance reduce, R1Raw material can be with 3,3 ', 4,4 '-hexichol Ketone tetracarboxylic dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 2,3,5,6- pyridine tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid two Acid anhydride, 3,4,9,10- tetracarboxylic dianhydride, meta-terphenyl -3,3 ', 4,4 '-tetracarboxylic dianhydride, para-terpheny -3,3 ', 4,4 '-four Carboxylic acid dianhydride, 1,1,1,3,3,3- hexafluoro -2,2- double (2,3- dicarboxyphenyi) propane dianhydride, 1,1,1,3,3,3- hexafluoro -2, Double (3,4- dicarboxyphenyi) propane dianhydride of 2-, double (2,3- dicarboxyphenyi) propane dianhydride of 2,2-, double (the 3,4- dicarboxyl of 2,2- Phenyl) propane dianhydride, double { 4 '-(2,3- di carboxyl phenyloxy) phenyl } propane dianhydride of 2,2-, double { 4 '-(the 3,4- dicarboxyl of 2,2- Phenoxy group) phenyl propane dianhydride, double { 4 '-(2,3- di carboxyl phenyloxy) phenyl } propane two of 1,1,1,3,3,3- hexafluoro -2,2- Double { 4 '-(3,4- di carboxyl phenyloxy) phenyl } propane dianhydride of acid anhydride, 1,1,1,3,3,3- hexafluoro -2,2-, 4,4 '-oxygen double neighbour benzene two Double O-phthalic acid dianhydride of formic acid dianhydride, 4,4 '-sulphonyl etc. is applied in combination.
R in formula (1)2It is the structure from the diamidogen as raw material.R in (a) composition, in formula (1)2Under being preferably State the divalent organic group represented by formula (2).
[changing 9]
(in formula (2), R5～R12It is each independently hydrogen atom, fluorine atom or monovalent organic group, R5～R12At least One is fluorine atom, methyl or trifluoromethyl.)
As R5～R12Monovalent organic group, such as carbon number 1～10 (preferably carbon number 1～6) can be enumerated Alkyl, the fluoroalkyl of carbon number 1～10 (preferably carbon number 1～6).
R in (a) composition, in formula (1)2Divalent organic group more preferably represented by following formula (3).During low-temperature setting Swelling have the tendency of in the polyimide precursor containing fluorine high using i line transmitance easily to produce.
[changing 10]
(in formula (3), R13And R14It is each independently fluorine atom or trifluoromethyl.)
R in (a) composition, in formula (1)2The ratio of the construction unit represented by formula (3) is preferably 1～100mol%, More preferably 10～100mol%, more preferably 30～100mol%.
As the structure represented by formula (2) or (3), 2,2 '-bis- (trifluoromethyl) -4 can be enumerated, 4 '-benzidine, 2, 2 '-bis- (fluorine) -4,4 '-benzidines, 4,4 '-diaminourea neighbour's fluorine biphenyl.They can be used alone or combine two or more Use.
Alternatively, it is also possible to the diamine compound using the structure providing in addition to formula (2), (3).For example can enumerate：To benzene Diamidogen, m-diaminobenzene., to xylylene amine, m-xylylene amine, 1,5- diaminonaphthalene, benzidine, 4,4 '-(or 3,4 '-, 3,3 '-, 2,4 '-, 2,2 ' -) diaminodiphenyl ether, 4,4 '-(or 3,4 '-, 3,3 '-, 2,4 '-, 2,2 ' -) diaminourea two Benzene sulfone, 4,4 '-(or 3,4 '-, 3,3 '-, 2,4 '-, 2,2 ' -) diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4 '-methylene-bis- (2,6- diethylaniline), 4,4 '-methylene-bis- (2,6- diisopropyl aniline), 2,4- diaminourea are equal Double { the 4- of trimethylbenzene, 1,5- diaminonaphthalene, 4,4 '-benzophenone diamidogen, double-{ 4- (4 '-amino-benzene oxygen) phenyl } sulfone, 2,2- (4 '-amino-benzene oxygen) phenyl } propane, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methane, 3,3 ', 5,5 '-tetramethyl - 4,4 '-diaminodiphenyl-methane, double { 4- (3 '-amino-benzene oxygen) phenyl } sulfone, 2,2- double (4- aminophenyl) propane, diamino Based polysiloxane etc..They can be used alone or are used in combination of two or more.
R in formula (1)3And R4It is each independently hydrogen atom, carbon number 1～20 (preferably carbon number 1～10, more Be preferably carbon number 1～6) alkyl, carbon number 3～20 (preferably carbon number 5～15, more preferably carbon number 6 ～12) cycloalkyl or the monovalent organic group with carbon carbon unsaturated double-bond.
As the alkyl of carbon number 1～20, methyl, ethyl, n-pro-pyl, 2- propyl group, normal-butyl etc. can be enumerated.As carbon The cycloalkyl of atomic number 3～20, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, adamantyl etc..
As the monovalent organic group with carbon carbon unsaturated double-bond, can enumerate and for example there is having of (methyl) acryloyl group Machine group.Specifically, the carbon number that can enumerate alkyl is 1～10 (methyl) acryloxyalkyl.In addition, " (first Base) acryloyl group " expression " methylacryloyl " or " acryloyl group ", " (methyl) acryloxy " expression " methacryl Epoxide " or " acryloxy ", " (methyl) acrylate " expression " methacrylate " or " acrylate ".
As alkyl carbon number be 1～10 (methyl) acryloxyalkyl, (methyl) acryloyl-oxy can be enumerated Base ethyl, (methyl) acryloxypropyl, (methyl) acryloxy butyl etc..
R3And R4At least one party be the monovalent organic group with carbon carbon unsaturated double-bond in the case of, by with utilization Active ray irradiates the compound combination producing free radical, thus formed can carry out molecule interchain linkage by radical polymerization Photosensitive polymer combination.
(a) composition of the present invention can be synthesized with diamidogen addition polymerization by making tetracarboxylic dianhydride.Furthermore it is possible to pass through formula (5), after the tetracarboxylic dianhydride represented by makes diester deriv, it is converted into the acyl chlorides represented by formula (6), and represented with formula (7) Diamine reactant and synthesize.Synthetic method can select from known method.
[changing 11]
(in formula (5), (6) and (7), R1～R4Identical with formula (1).)
With regard to the molecular weight of the polyimide precursor as (a) composition, preferably by the Weight-average molecular of polystyrene conversion Measure as 10000～100000, more preferably 15000～100000, more preferably 20000～85000.If Weight-average molecular Amount is more than 10000, then can fully reduce the stress after solidification.In addition, if being less than 100000, then can improve further Dissolubility in solvent, the viscosity of solution reduces, and operability improves.In addition, weight average molecular weight can pass through gel permeation chromatography Method is measured, and can be converted by using polystyrene standard standard curve and obtain.
During synthesis (a) composition, tetracarboxylic dianhydride and the mol ratio of diamidogen are usually 1.0, but for control molecular weight, end The purpose of residue or the mol ratio of 0.7～1.3 scope.It is less than or equal to 0.7 in mol ratio or be more than or equal to In the case of 1.3, the molecular weight of the polyimide precursor of gained diminishes, and the low stress after solidification is possible to insufficient performance.
As to the present invention as (a) composition polyimide precursor carry out heat treated and carry out imidizate thus It is translated into the heating-up temperature of polyimides, preferably 80～300 DEG C, more preferably 100～300 DEG C, more preferably 200～ 300℃.During less than 80 DEG C, imidizate is insufficient to be carried out, and thermostability is likely to decrease, if entered in the temperature higher than 300 DEG C Row is it is likely that can cause to semiconductor element to damage.
Polyimide precursor represented by formula (1) is coated base material and the remnants of cured film obtained by being heating and curing Stress is preferably less than or equal to 30MPa, more preferably less than or equal to 27MPa when the thickness of cured film is 10 μm, enters one Step is preferably less than or equal to 25MPa.If residual stress is less than or equal to 30MPa, in the thickness after to solidify for 10 μm Mode when forming film, can more fully suppress the warpage of chip, can more suppress to fix in the transport of chip, absorption The undesirable condition of middle generation.
In addition, residual stress can measure device FLX-2320 (KLA Tencor company system) by using membrane stress surveying After determining the amount of warpage of chip, it is converted into the method for stress to measure.
Form, in the way of being 10 μm for the thickness after to solidify, the cured film obtaining in the present invention, by above-mentioned resin group Compound is coated on substrate and is dried and after forming the operation of film, the thickness of film is necessary for 20 μm about.Therefore, with profit In the case of irradiating the compound combination producing free radical with active ray and forming photosensitive polymer combination, resin combination I line transmitance more high more preferred.
Specifically, during 20 μm of thickness, i line transmitance is preferably greater than or equal to 5%, more preferably greater than or equal to 8%, further preferably greater than or equal to 15%.If less than 5%, then i line can not reach deep, the insufficient product of free radical Raw, when therefore developing, resin oozes out from the substrate of film, and photobehavior is likely to decrease.
In addition, i line transmitance can use U-3310 spectrophotometer (HITACHI company system), surveyed by transmission UV spectrum Fixed.
(b) composition：There is ethylene unsaturated group and the photopolymerizable compound of isocyanuric acid ring structure
The resin combination of the present invention comprises the optical polymerism with ethylene unsaturated group and isocyanuric acid ring structure Compound is as (b) composition.It is believed that：Above-mentioned photopolymerizable compound works as cross-linking agent, also remains in film after solidification In such that it is able in polyimide curing film formed cross-linked structure, suppression swelling.In addition, photopolymerizable compound has carrying The function of the orientation of high polyimide curing film is it is also possible to improve the residual film ratio after solidification.
In addition, as the swelling additive of suppression polyimide curing film, having aluminium chelate compound, if but e.g., less than or Adding aluminium chelate compound during low-temperature setting equal to 300 DEG C then cannot sufficient effect.By using above-mentioned (b) composition, even if It is that low-temperature setting less than or equal to 300 DEG C also can obtain sufficiently swelling inhibition.
As above-mentioned photopolymerizable compound, preferably Triallyl isocyanurate, Triallyl isocyanurate pre-polymerization Thing and the compound with the structure represented by following formula (4).
[changing 12]
(in formula (4), R24For hydrogen atom or methyl, X is alkylidene, and n is 1～25 integer.)
The compound with the structure represented by formula (4) is preferably the compound represented by following formula (5).
[changing 13]
(in formula (5), R21～R23It is each independently monovalent organic group, at least one is represented by above-mentioned formula (4) Group.)
Compound as the structure having represented by formula (4), it is possible to use the compound represented by following formula (6).
[changing 14]
(in formula (6), R21～R23It is each independently monovalent organic group, at least one is represented by following formula (9) Group.)
[changing 15]
(in formula (9), R24For hydrogen atom or methyl, X is alkylidene, and Y is alkylidene, and n is 1～25 integer, and m is 1～14 Integer.)
As the monovalent organic group of formula (5) and (6), the alkyl of carbon number 1～15, glycidyl, second can be enumerated Thiazolinyl etc..The alkyl of carbon number 1～15 can also have halogen atom as such as 2,3 dibromopropyls.
As the carbon number of formula (4) and the alkylidene of X and Y of (9), be not particularly limited, preferably carbon number 2～ 7 alkylidene, the more preferably alkylidene of carbon number 2～4, more preferably ethylidene or propylidene.
The n of formula (4) and formula (9) is 1～25 integer, preferably 1～20 integer, more preferably 1～15 integer.
M in formula (9) is 1～14 integer, preferably 1～6 integer, more preferably 6 integer.
It is the concrete example of photopolymerizable compound as (b) composition, the compound represented by following formula (10) can be enumerated, on State compound to buy as A-9300 (Xin Zhong village chemical industry Co. Ltd. system).
[changing 16]
From the viewpoint of swelling inhibition and film physical property, the content of (b) composition of the resin combination of the present invention is relatively It is preferably 1～50 mass parts, more preferably 1～30 mass parts, more preferably 5～20 mass in (a) composition 100 weight portion Part.
By the content of (b) composition is set to, more than or equal to 1 mass parts, can press down with respect to (a) composition 100 weight portion Cured film processed by organic solvent cause swelling, by being set to less than or equal to 50 mass with respect to (a) composition 100 weight portion Part, the reduction of cured film elongation can be suppressed.
(c) composition：Produce the compound of free radical using active ray
The resin combination of the present invention preferably comprises and produces the compound of free radical as (c) composition by the use of active ray.
R in the formula (1) of the polyimide precursor of (a) composition3And/or R4At least a portion be that to have carbon carbon unsaturated double During the monovalent organic group of key, comprise (c) composition by making resin combination, the resin combination of the present invention can be made sense Photosensitive resin composition.
As (c) composition, for example, can enumerate：Oxime ester compound described later, benzophenone, N, N '-tetramethyl -4,4 '-two The N such as aminobenzophenone (michaelis ketone), N '-tetraalkyl -4,4 '-diaminobenzophenone；
2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2- methyl isophthalic acid-[4- (methyl mercapto) benzene Base] -2- morpholino-acetone -1 grade aromatic ketone；
The quinones of alkyl-anthraquinone etc. and aromatic rings contracting ring；The benzoin ether compound such as benzoin alkylether, benzoin, The benzoin compound such as alkyl benzoin；The benzil derivatives such as benzil dimethyl ketal.They can be used alone also may be used To be used in combination of two or more.
Wherein, because light sensitivitys are excellent and provide good pattern, therefore preferred oxime ester compound.
Oxime ester compound be preferably following formula (9) represented by compound, the compound represented by following formula (10) or under State the compound represented by formula (11).
[changing 17]
(in formula (9), R and R1The alkyl of expression carbon number 1～12, the cycloalkyl of carbon number 4～10, phenyl respectively Or tolyl, the preferably alkyl of carbon number 1～8, the cycloalkyl of carbon number 4～6, phenyl or tolyl, more preferably The alkyl of carbon number 1～4, the cycloalkyl of carbon number 4～6, phenyl or tolyl, more preferably methyl, cyclopenta, Phenyl or tolyl.
R2Represent H, OH, COOH, O (CH2)OH、O(CH2)2OH、COO(CH2) OH or COO (CH2)2OH, preferably H, O (CH2)OH、O(CH2)2OH、COO(CH2) OH or COO (CH2)2OH, more preferably H, O (CH2)2OH or COO (CH2)2OH.)
[changing 18]
(in formula (10), R3Represent the alkyl of carbon number 1～6, preferably propyl group respectively.
R4Represent NO2Or ArCO (here, Ar represents substituted or unsubstituted aryl.), as Ar, preferably tolyl.
R5And R6Represent alkyl, phenyl or the tolyl of carbon number 1～12, preferably methyl, phenyl or toluene respectively Base.)
[changing 19]
(in formula (11), R7Represent the alkyl of carbon number 1～6, preferably ethyl.
R8For having the organic group of acetal key, preferably have with the compound shown in formula described later (11-1) R8Corresponding substituent group.In addition, replace thering is R8Phenyl ring can have substituent group further.
R9And R10Represent alkyl, phenyl or the tolyl of carbon number 1～12, preferably methyl, phenyl or toluene respectively Base, more preferably methyl.)
As the compound represented by above-mentioned formula (9), for example, can enumerate compound represented by following formula (9-1) and following Compound represented by formula (9-2).Wherein, the compound represented by following formula (9-1) can be used as IRGACURE OXE-01 (BASF Co. Ltd. system, trade name) obtains.
[changing 20]
As the compound represented by above-mentioned formula (10), for example, can enumerate the compound represented by following formula (10-1).Should Compound can obtain as DFI-091 (DAITO CHEMIX Co. Ltd. system, trade name).
[changing 21]
As the compound represented by above-mentioned formula (11), for example, can enumerate the compound represented by following formula (11-1).Energy Enough obtain as ADEKA OPTOMER N-1919 (Asahi Denka Co., Ltd.'s system, trade name).
[changing 22]
As other oxime ester compounds, preferably use following compounds.
[changing 23]
In addition, as (c) composition, it is possible to use following compound.
[changing 24]
As containing content during (c) composition, it is preferably 0.01～30 mass parts with respect to (a) composition 100 mass parts, more It is preferably 0.05～15 mass parts, more preferably 0.1～10 mass parts.If use level is more than or equal to 0.01 mass Part, then exposure portion is crosslinked abundant, and photobehavior becomes more good, by for less than or equal to 30 mass parts, having cured film Thermostability improve tendency.
(d) composition：Solvent
The resin combination of the present invention can include the solvent as (d) composition.
It is solvent as (d) composition, preferably completely dissolve the polar solvent of polyimide precursor, N- methyl -2- can be enumerated Ketopyrrolidine, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethyl phosphoric acid trigalloyl Amine, gamma-butyrolacton, δ-valerolactone, gamma-valerolactone, Ketohexamethylene, Ketocyclopentane, propylene glycol monomethyl ether, polypropylene carbonate Ester, ethyl lactate, 1,3- dimethyl-2-imidazolinone etc..
These solvents may be used singly or in combination of two or more use.
The content of (d) composition of the resin combination of the present invention is preferably 50～500 with respect to (a) composition 100 weight portion Mass parts, more preferably 80～400 mass parts, more preferably 100～300 mass parts.
(e) composition：Photopolymerizable compound beyond (b) composition
The resin combination of the present invention can comprise (b) composition beyond photopolymerizable compound as (e) composition.As Above-mentioned photopolymerizable compound, can enumerate diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, four Ethylene glycol bisthioglycolate (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) propylene Acid esters, 1,4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, tetramethylolmethane three (methyl) third Olefin(e) acid ester, tetramethylolmethane four (methyl) acrylate, styrene, divinylbenzene, 4- vinyltoluene, 4-vinylpridine, NVP, (methyl) acrylic acid 2- hydroxy methacrylate, 1,3- (methyl) acryloxy -2- hydroxy propane, methylene Base bisacrylamide, N, N- DMAA, N hydroxymethyl acrylamide etc..They can be used alone it is also possible to group Close two or more uses.
It is preferably set to 1～100 mass containing use level during photopolymerizable compound with respect to (a) composition 100 mass parts Part, more preferably it is set to 10～75 mass parts, be further preferably set to 30～50 mass parts.If use level is more than or equal to 1 matter Amount part, then can give better photobehavior, if less than or be equal to 100 mass parts, then can more improve solidification The thermostability of film.
In addition to above-mentioned (a)～(e) composition, in order to ensure good storage stability, the resin combination of the present invention Radical polymerization inhibitor or radical polymerization inhibitor can also be comprised.
Specifically, can enumerate p methoxy phenol, diphenyl 1,4-benzoquinone, benzoquinone, hydroquinone, 1,2,3,-thrihydroxy-benzene, phenothiazine, Benzodiazepiness, o-dinitrobenzene, paradinitrobenzene, meta-dinitro-benzent, phenanthrenequione, N- phenyl -2- naphthylamine, copperon, 2,5- methyl Benzoquinone, tannic acid, to benzylamino phenol, nitrosamine compound etc..They may be used singly or in combination of two or more Use.
Contain content when radical polymerization inhibitor or radical polymerization inhibitor as resin combination, become with respect to (a) 100 mass parts are divided to be preferably 0.01～30 mass parts, more preferably 0.01～10 mass parts, more preferably 0.05～5 matter Amount part.If use level is more than or equal to 0.01 mass parts, storage stability becomes more good, if less than or be equal to 30 Mass parts, then can more improve the thermostability of cured film.
In order that more improving to the adaptation of silicon substrate etc. after solidification, the resin combination of the present invention can wrap further Containing organic silane compound.
As above-mentioned organic silane compound, gamma-amino propyl trimethoxy silicane, gamma-amino propyl group three second can be enumerated TMOS, VTES, vinyltrimethoxy silane, γ-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-(methyl) acryloxypropyl trimethoxy silane, 3- urea propyl group three Ethoxysilane, 3-mercaptopropyi trimethoxy silane, 3- isocyanates propyl-triethoxysilicane, double (2- ethoxy) -3- Aminopropyltriethoxywerene werene, triethoxysilylpropyltetrasulfide ethyl carbamate, 3- (triethoxysilyl) Propylsuccinic anhydride, phenyl triethoxysilane, phenyltrimethoxysila,e, N- phenyl -3- TSL 8330, 3- triethoxysilyl-N- (1,3- dimethylbutylene) propylamine, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silicon Alkane etc..
As long as the content of organic silane compound is suitably adjusted to is obtained in that desired effect.
＜ cured film and manufacture method ＞ of pattern cured film
The compositionss of the present invention are coated base material and the residual stress of cured film obtained by being heating and curing is in solidification The thickness of film is to be preferably less than or equal to 30MPa, more preferably less than or equal to 27MPa when 10 μm, more preferably little In or be equal to 25MPa.If residual stress is less than or equal to 30MPa, in the way of the thickness after solidification is 10 μm, form film When, can more fully suppress the warpage of chip, that can more suppress to produce in the transport of chip, absorption are fixing is bad Situation.
In addition, residual stress can measure device FLX-2320 (KLA Tencor company system) by using membrane stress surveying After determining the amount of warpage of chip, it is converted into the method for stress to measure.
The pattern cured film of the present invention is the pattern cured film being formed by above-mentioned resin combination.The pattern solidification of the present invention Film can be formed when above-mentioned resin combination contains (c) composition.
In addition, the manufacture method of the pattern cured film of the present invention comprises：Above-mentioned resin combination is coated on substrate simultaneously It is dried and form the operation of film；Above-mentioned film is irradiated after active ray, is developed and obtained the operation of patterned resin film； And above-mentioned patterned resin film is carried out with the operation of heat treated.
Hereinafter, first each operation of the manufacture method of pattern cured film is illustrated.
The manufacture method of the pattern cured film of the present invention comprise above-mentioned resin combination is coated on substrate and be dried and Form the operation of film.Method as being coated on resin combination on substrate, can enumerate infusion process, nebulization, screen printing Brush method, spin-coating method etc..As base material, silicon wafer, metal basal board, ceramic substrate etc. can be enumerated.The resin combination energy of the present invention Enough form the cured film of low stress, therefore, it is possible to be particularly suitable for the bigbore silicon wafer more than or equal to 12 inches.
In drying process, removed by heating solvent, the film of non-adhesiveness can be formed.Drying process can use The devices such as DATAPLATE (Digital Hotplate, PMC company system), as baking temperature, preferably 90～130 DEG C, as dry The dry time, preferably 100～400 seconds.
The manufacture method of the pattern cured film of the present invention comprises to irradiate active ray to the film being formed by above-mentioned operation Afterwards, developed and obtained the operation of patterned resin film.Thus, it is possible to obtain the resin film defining expected pattern.The present invention Resin combination be suitable for i line exposing, as irradiate active ray, it is possible to use ultraviolet, far ultraviolet rayss, visible ray Line, electron ray, X-ray etc..
As developer solution, it is not particularly limited, the anti-flammability solvents such as 1，1，1-trichloroethane can be used；Sodium carbonate is water-soluble The aqueous alkalis such as liquid, tetramethylammonium hydroxide aqueous solution；N,N-dimethylformamide, dimethyl sulfoxide, N, N- dimethylacetamide The good solvents such as amine, METHYLPYRROLIDONE, Ketocyclopentane, gamma-butyrolacton, acetate esters；These good solvents and lower alcohol, water, Mixed solvent of the poor solvents such as aromatic hydrocarbon etc..It is rinsed using poor solvent etc. as needed after development.
The manufacture method of the pattern cured film of the present invention comprises patterned resin film is carried out with the operation of heat treated.
This heat treated can use the device such as vertical diffusion furnace (silver dollar Lindberg system), preferably heating-up temperature 80～ 300 DEG C are carried out, and heat time heating time is preferably 5～300 minutes.By this operation, can obtain making the polyamides in resin combination sub- Amine precursor carries out imidizate and the pattern cured film containing polyimide resin.
In addition, the cured film of the present invention is the cured film being formed by above-mentioned resin combination.That is, the present invention's consolidates Changing film can also be the cured film being unpatterned.
The cured film of the present invention being achieved in that or pattern cured film can act as the sealer of semiconductor device, layer Between insulating barrier, again wiring layer etc..
Fig. 1 is the outline section of the semiconductor device again with distribution structure as an embodiment of the invention Figure.
The semiconductor device of present embodiment has multi-layer wiring structure.Shape on interlayer insulating film (interlayer dielectric) 1 Become to have Al wiring layer 2, be formed further with insulating barrier (dielectric film) 3 (such as P-SiN layer) at an upper portion thereof, and be formed further with The sealer (surface protection film) 4 of element.Initially form wiring layer 6 again from the cushion part 5 of wiring layer 2, and extend until The top of core 8, described core 8 is the coupling part with the conductive ball 7 being formed by solder, gold etc. as external connection terminals. Seal coat 9 is formed with further on sealer 4.Wiring layer 6 is connected with conductive ball 7 across barrier metal 10 again, In order to keep this conductive ball 7 to be provided with collar (collar) 11.When installing the encapsulation of this structure, in order to relax further Stress, also sometimes across underfill 12.
The cured film of the present invention or pattern cured film can be used in above-mentioned embodiment seal coat material, again distribution use The balls such as core material, solder collar material, underfill etc..
The electronic unit of the present invention is except having the seal coat, again of the cured film employing the present invention or pattern cured film It is not particularly limited beyond underfill etc. used in the ball collar of distribution core, solder etc., flip-chip etc., can adopt Use various structures.
Embodiment
Hereinafter, the present invention is illustrated by embodiment.
Synthesis example 1 (synthesis of Pyromellitic Acid-hydroxyethyl methacrylate diester)
In 0.5 liter of polyethylene bottle, the pyromellitic acid anhydride of 24 hour will be dried using 160 DEG C of drying machine 43.624g (200mmol), methacryloxyethyl acid 2- hydroxy methacrylate 54.919g (401mmol) and hydroquinone 0.220g are dissolved in 394g In N-Methyl pyrrolidone, after adding 1, the 8- diazabicyclo endecatylene of catalytic amount, (25 DEG C) stirrings 24 are little at room temperature When, it is esterified, thus obtaining Pyromellitic Acid-hydroxyethyl methacrylate two ester solution.This solution is set to PMDA (HEMA) solution.
Synthesis example 2 (synthesis of 4,4 '-oxygen bisphthalate)
In 0.5 liter of polyethylene bottle, the 4 of 24 hours will be dried using 160 DEG C of drying machine, 4 '-oxygen double neighbour benzene two Formic acid 49.634g (160mmol), methacryloxyethyl acid 2- hydroxy methacrylate 44.976g (328mmol) and hydroquinone 0.176g are dissolved in In 378g N-Methyl pyrrolidone, after adding 1, the 8- diazabicyclo endecatylene of catalytic amount, (25 DEG C) stirrings at room temperature 48 hours, it is esterified, obtained 4, double phthalic acid-hydroxyethyl methacrylate two ester solution of 4 '-oxygen.This solution is set For ODPA (HEMA) solution.
Synthesis example 3 (synthesis of polymer 1)
PMDA (HEMA) solution that synthesis example 1 obtains is added in 0.5 liter of flask possess blender, thermometer ODPA (HEMA) the solution 58.652g that 195.564g and synthesis example 2 obtain, afterwards, under ice-cooling so that reaction solution temperature The mode remaining less than or being equal to 10 degree uses Dropping funnel Deca thionyl chloride 25.9g (217.8mmol).Thionyl chloride drip Plus after terminating, carry out reaction in 2 hours under ice-cooling, obtain PMDA (HEMA) and the solution of acid chloride of ODPA (HEMA).Then, make With Dropping funnel, note making the temperature of reaction solution to comprise 2,2 '-bis- (three less than 10 DEG C of Deca under ice-cooling Methyl fluoride) benzidine 31.696g (99.0mmol), pyridine 34.457g (435.6mmol), hydroquinone 0.076g (0.693mmol) N-Methyl pyrrolidone solution 90.211g.This reactant liquor is instilled in distilled water, precipitate is collected by filtration, carries out drying under reduced pressure, Thus obtaining poly amic acid ester.It is 34,000 by the weight average molecular weight that polystyrene standard conversion is obtained.It is set to be polymerized Thing 1.1g polymer 1 is made to be dissolved in 1.5g N-Methyl pyrrolidone, by spin application on the glass substrate, at 100 DEG C On hot plate, heating makes solvent volatilize for 180 seconds, forms the film of 20 μm of thickness.Now, the i line transmitance of obtained film is 30%.
The condition determination that polymer 1 passes through the weight average molecular weight that the conversion of GPC method polystyrene standard is obtained is as follows, using phase Polymer 0.5mg, the solution for 1mL for the solvent [THF/DMF=1/1 (volumetric ratio)] are measured.
Measure device：Detector Hitachi Co., Ltd L4000UV
Pump：Hitachi Co., Ltd L6000
Shimadzu Scisakusho Ltd C-R4A Chromatopac
Condition determination：Post Gelpack GL-S300MDT-5 × 2 piece
Eluant：THF/DMF=1/1 (volumetric ratio)
LiBr(0.03mol/L)、H3PO4(0.06mol/L)
Flow velocity：1.0ml/min
Detector：UV270nm
The i line transmitance of polymer 1 is measured using U-3310 spectrophotometer (HITACHI company system).
Embodiment 1-6 and comparative example 1-4
Each composition of (a), (b), (c), (e) is dissolved in N-Methyl pyrrolidone with the cooperation shown in table 1, modulates resin Compositionss, evaluate resolution, residual stress and swelling ratio by following methods.Show the result in table 1.
In addition, in table 1, the numeral in the parantheses on (b) and each hurdle of (c) composition represents with respect to (a) composition 100 mass parts Addition (mass parts).In addition, solvent uses N-Methyl pyrrolidone, usage amount both with respect to (a) composition 100 mass parts with 1.5 times (150 mass parts) use.
(evaluation of photobehavior (resolution))
By spin-coating method, the above-mentioned resin combination modulated is coated on 6 inch silicon wafer, on 100 DEG C of hot plate Heating 3 minutes, makes solvent volatilize, obtains the film of 10 μm of thickness.This film be impregnated in gamma-butyrolacton:Butyl acetate=7:3 Mixed solvent in, by until 2 times of time be completely dissolved are set as developing time.For obtained by same method Film, across photomask, using i line stepping exposure machine FPA-3000iW (Canon Co., Ltd's system), carries out being scaled with i line 300mJ/cm2Exposure, by water immersion in gamma-butyrolacton:Butyl acetate=7:In 3, after carrying out sheathed dip-type developing, use Ketocyclopentane is rinsed.The minima being possible to the mask size of live width/intermittent pattern of resolution is evaluated as resolution.
(mensure of residual stress)
The resin combination of gained is coated on 6 inch silicon wafer by spin-coating method, 100 DEG C of hot plate heats 3 Minute, so that solvent is volatilized, after being solidified, thickness is 10 μm of film.It is used for vertical diffusion furnace (silver dollar Lindberg System), it is heating and curing 4 hours with 270 DEG C under nitrogen atmosphere, obtain polyimide film.The remnants of the polyimide film after solidification should Power uses membrane stress to measure device FLX-2320 (KLA Tencor company system) in room temperature measuring.
(mensure of swelling ratio)
The resin combination of gained is coated on 6 inch silicon wafer by spin-coating method, 100 DEG C of hot plate heats 3 Minute, so that solvent is volatilized, after being solidified, thickness is 10 μm of film.It is used for vertical diffusion furnace (silver dollar Lindberg System), it is heating and curing 4 hours with 270 DEG C under nitrogen atmosphere, obtain polyimide film.The polyimide film that will make on substrate Impregnated in 70 DEG C of N-Methyl pyrrolidone, carry out heating in 20 minutes.The sample that impregnated in N-Methyl pyrrolidone is distilled After water washing, measure thickness.Thickness Variation before and after being impregnated by N-Methyl pyrrolidone calculates swelling ratio (%).
[table 1]
In table 1, (b) composition is as follows.
A9300 (ethoxylation isocyanuric acid triacrylate, KCC of Xin Zhong village system, trade name)
In table 1, (c) composition is following compounds.
C1：1,2- acetyl caproyl, 1- [4- (thiophenyl) phenyl-, 2- (o- benzoyl oxime)] (BASF Co. Ltd. system, commodity Name " IRGACURE OXE-01 ")
C2：Adeka Cruise NCI-930 (Asahi Denka Co., Ltd.'s system, trade name)
In table 1, (e) composition is TEG dimethylacrylate.
In addition, aluminium chelate compound A (w) is praseodynium aluminum (fine chemistry company system is ground in river).
In embodiment, by adding the compound with isocyanuric acid skeleton in the polyimides containing the rigidity of fluorine, Thus in the state of maintaining less than or equal to the low stress of 30MPa, swelling ratio is less than or equal to 10%.On the other hand, than Compared with example, do not contain the compound with isocyanuric acid skeleton in compositionss in the case of, fluorinated polyimide be more than or equal to 20% big swelling ratio.In addition, although with the addition of aluminium chelate compound in comparative example 3 and 4, but because solidification temperature is low, therefore not Obtain reagent resistance improvement.
Industrial applicibility
The resin combination of the present invention can be used in forming the seal coat materials of electronic unit such as semiconductor device, joins The so-called encapsulation purposes such as the balls such as line core material, solder collar material, underfill.
Above-mentioned several embodiments of the invention and/or embodiment are described in detail, but those skilled in the art easily exist In the case of new teaching without materially departing from the present invention and effect, these embodiments illustrated and/or embodiment are applied to be permitted Many changes.Therefore, these many changes are also contained in the scope of the present invention.
Japanese publication explanation using the document described in this description and the Paris Convention priority basis as the application The content of book is fully incorporated in this.

Claims (15)

1. a kind of resin combination, it comprises following (a) composition and (b) composition,
A () has the polyimide precursor of the construction unit represented by following formula (1),
In formula, R1For quadrivalent organic radical group, R2For divalent organic group, R3And R4Be each independently hydrogen atom, carbon number 1～ 20 alkyl, the cycloalkyl of carbon number 3～20 or the monovalent organic group with carbon carbon unsaturated double-bond,
B () has ethylene unsaturated group and the photopolymerizable compound of isocyanuric acid ring structure.
2. resin combination according to claim 1, the R of described formula (1)2Divalent organic base represented by following formula (2) Group,
In formula, R5～R12It is each independently hydrogen atom, fluorine atom or monovalent organic group, R5～R12At least one be fluorine Atom, methyl or trifluoromethyl.
3. resin combination according to claim 1 and 2, the R of described formula (1)2Bivalence represented by following formula (3) has Machine group,
In formula, R13And R14It is each independently fluorine atom or trifluoromethyl.
4. the resin combination according to any one of claims 1 to 3, described photopolymerizable compound comprises following formula (4) structure represented by,
In formula, R24For hydrogen atom or methyl, X is alkylidene, and n is 1～25 integer.
5. resin combination according to claim 4, described photopolymerizable compound is the chemical combination represented by following formula (5) Thing,
In formula, R21～R23It is each independently monovalent organic group, at least one is the group represented by described formula (4).
6. the resin combination according to any one of Claims 1 to 5, described (b) composition is with respect to described (a) composition 100 mass parts comprise 0.01～50 mass parts.
7. the resin combination according to any one of claim 1～6, it comprises to irradiate product using active ray further The compound of raw free radical is as (c) composition.
8. resin combination according to claim 7, described utilization active ray irradiates and produces the compound of free radical and be Oxime ester compound.
9. the resin combination according to any one of claim 1～8, comprises the photopolymerization beyond (b) composition further Property compound is as (e) composition.
10. resin combination according to claim 9, described photopolymerizable compound is (methyl) acyclic compound.
A kind of 11. manufacture methods of cured film, it comprises：Resin combination any one of claim 1～10 is applied Cloth and is dried and forms the operation of film and the operation that described film is carried out with heat treated on substrate.
A kind of 12. manufacture methods of pattern cured film, it comprises：By the resin combination any one of claim 1～10 Thing is coated on substrate and is dried and forms the operation of film；Described film is irradiated after active ray, is developed and obtain The operation of patterned resin film；And described patterned resin film is carried out with the operation of heat treated.
A kind of 13. cured film, are obtained by the manufacture method of the cured film described in claim 11.
A kind of 14. pattern cured films, are obtained by the manufacture method of the pattern cured film described in claim 12.
A kind of 15. electronic units, it has the pattern cured film described in cured film or claim 14 described in claim 13.
CN201580008033.3A 2014-02-10 2015-01-28 Resin composition containing polyimide precursor, method for manufacturing cured film, and electronic component Pending CN106462065A (en)

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